Process for the continuous regeneration of a granular catalyst



J ly 1 5 R. E. GODDARD 2,897,157

PROCESS FOR THE CONTINUOUS REGENERATION OF A GRANULAR CATALYST Filed, June 12, 1953 l6 Inventor Attorney PROCESS FOR THE CONTINUOUS REGENERA- TION OF A GRANUIJAR'CATALYST Application June 12, 1953, SerialNo. 361,327

Claims priority, application Great Britain July 11, 1952 e 3 Claims. (Cl. 252-418) This invention relates to processes for the production of hydrocarbons by catalytic conversion and especially to such processes conducted in the vapour phase.

It is known in hydrocarbon conversion process using, for example: silica/ alumina, or silica and/or alumina in combination with other oxides; and other .metal oxide catalysts, to employ the catalyst in the form of granules and to pass hydrocarbons togetherwith amoving body of catalyst granules through areactor, which istmaintained under appropriate conditions of temperature and pressure. The catalyst in a short time becomes coated with .carbonaceous deposits resultingegfrom polymerisation and requires to be regenerated, which is commonly done by treatment with an oxidising gas outside the reactor.

In one form of this process thecatalyst granulesmove through the reactor under the effect of gravity and the present invention, while of wide application, is ofespecial value in relation to this process.

According to the present invention granular catalyst coated with carbonaceous materialflows preferably under gravity to a zone in which it is treated with .an inert gas to free it from reactants and thereafter to a series of regeneration stages in each of which it is brought -into-.contact in co-current flow with an oxidising gas of such .a composition, in such proportion and at such a temperature, that the amount of carbonaceous material burnt ofl and the temperature in each stage is controlled Within predetermined limits. The particular benefits of the invention are maintenance of high catalytic activity and good heat conversion. There are also the attendant advantages of: consistency in the composition of the prodnot; smooth operation over long periods resulting in improved output; and savings in equipment.

Preferably there are'in each stage gas distributing and gas disengaging devices comprising a series of ,parallel conduits situated at the top and bottom of the vessel in which the stage is conducted. Preferably, also, each of these vessels is cylindrical with top and bottom conical portions, and the gas distributing and disengaging devices are located in horizontal partitions situated at the topand bottom of the cylindrical portion of the regeneration vessel.

One especially important application of. the process of the invention is to xylene isomerization and the invention will now be described with respect to that process, although it is to be understood that his suitable for use in the regeneration of catalysts in a wide variety of chemical processes. For isomerization to p-xylene suitable feed materials are e.g. xylene or xylene mixtures comprising material having the following range of composition (the sum of ethyl benzene and non-aromatics'lying United States Patent within 4 to 40% of the whole):

Percentby weight p-Xylene 01-15 mand o-Xylene 45-80 Ethylbenzene 3-35 Non-aromatics '1-5 In a process of this type the'maximum'amount of car- 2,897,157, Patented July 28, 1950 be maintained is about 2%, and if high activity is to be maintained about 1.0% by weight'of'the catalyst granules. In a typical process the total weight of carbon to be removed during regeneration is of the order of 15 kilograms per hour, which is equivalent to tonne calories per hour when the carbonaceous material is burnt. In this case it is preferred to operate in 4 stages of regeneration, .(i) because greateriflexibility of temperature control is achieved, and (ii) because .the heat developed .can be usefully and efficiently used, eg for preheating the main reactants, or the oxidizing gases used 'for regeneration of the catalyst. 1

Each of the 4 regenerating vessels is provided at the upper end with a gas distributing device comprising a short section fitted with a number of downcomers for the catalyst beads and at the lower-end of its cylindrical portion with a similar gas/solid disengagement section. Warm oxidising medium is fed through a pipe to the gas distribution section of each vessel, and the medium used in that vessel is taken ofi at the disengagementisection thereof. .The granules and oxidising medium, therefore, flow co-currently in each vessel, which arrangementhas the advantages that the oxidising medium is at its lowest temperature where it meets the catalyst .most heavily loaded with carbon, and the catalyst and oxidising medium leave each vessel at maximum temperature,'thus absorbing themaximum heat of reaction.

The preheated oxidising medium is fed to the arrangement in two streams, one for the top three .vessels being introduced to the gas distribution device of the third vessel, and the second to the gas distribution device of the fourth vessel.

The first stream containing 21% oxygen enters the top of the third vessel at about 400 C. and reduces the carbon content of the beads therein from about 0.2% to about 0.05% by Weight. After disengagement from the heads at the bottom of the third vessel the regenerating medium passes via a cooling element, for example a finned conduit but preferably a heat exchanger, in order to reduce its temperature, to the top of thesecond vessel, which it enters with an oxygen content of 20.3% and at about 350 C. In this second vessel the carbon content of the beads is reduced from about 0.4% to 0.2% 'by weight. The regenerative medium after disengagement from the beads at the bottom of the second vessel passes via a heat exchanger, in which it is cooled, to the top of the first vessel, which it enters with an oxygen content'of about 18.3% and at about 350 C. In this first vessel it is'brought to about 550 C. and the carbon contentof the beads is there reduced from about 1% to about 0.4%.

The second stream comprising air is fed to the top 70f the fourth vessel at 450-500 C. and is there. brought into contact with the descending stream of beads con taining about 0.05% carbon and at about 550 'C. In this vessel the beads are substantially freed from carbon and leave it in suitable condition'for returnto the iso: merization reactor feed hopper, to which they are trans* ported as an entrained stream by a gas lift employing,

for example, the disengaged gas emergingfrom the fourth vessel.

In;order to prevent leakage of airor oxidising gas into the reaction zone there are 'two nitrogen inlets; the first between the catalyst surge drum and the reaction vessel; and the second between the reaction zoneand the first regenerating vessel, preferably at the bottom of the hydro: carbon stripping zone. The second nitrogen stream, which is of larger volume is employed as the agent {for removing hydrocarbon and more volatile. tars from the granules in the stripping'zone. V Preferably in the isomerizationreaction zone the flow of catalyst granules and reactant is countercurrent to one another, since, in this way, the largely converted material is brought into contact with the freshly regenerated, and therefore most active, catalyst. As a further feature of the invention, therefore, the novel regenerating process is employed in combination with a reaction zone in which rent. The catalyst of the present invention may be in the form of granules prepared by various methods such as grinding and grading suitable composites, which may be synthetic or of natural origin; or .by pelleting under pressure such composites. A very suitable form of granules is the socalledbeads, Whatever, the form of lgranule it is desirable .thatit should be as robust and resistant to attritionas possible. A suitable size of granule is 1 to 14', preferably /s" to A A suitable arrangement for conducting the invention is theflow of catalyst granules and reactants is countercuris reduced from 1% to about 0.4% therein. The gas leaving vessel 1 by line 27 is at about 550 C. and may be passed through an exchanger for recovery of some of its heat if desired.

The inlet temperature toeach of the vessels 1, 2, 3 and 4, is controlled so that the exit temperature in each'case is approximately 550C. It is desirable not to heat the catalyst above- 550 C. because its activity would thereby bedecreased. It is found vthat a gas inlet temperature ofabout 350 C.'is suitable for regenerators 1 and 2.

The second stream of regenerating gas enters vessel 4 at about 450 to 500 C and travels therethrough co-currently with the descending stream of granules which at their entry contain about 0.05% carbon and are at about 550 C. Substantially all of the carbon is thus burnt off and the granulesfall by gravity through pipe 28 to the gas lift 18 which is'supplied with spent regenerating gas through line 29. From 18 the carbon free granules shown in the accompanying drawing, which is schematic and in which numerals 1, 2 and 3 represent three regencrating vessels, each provided at the top with a gas distributing devicecomprising a plate 5 and a number of short pendant downcomers 6, and a similar gas disengagement.devicejcomprising plate 7 and downcomers 8;v

4v is a larger. regenerating vessel similarly provided with gas distributing and separating devices; 9 and 10 heat exchangers; 11' an isomerization reactor fitted with gas distributing and disengaging devices and with an extension 12 for stripping adsorbed hydrocarbons and more volatile tars from the granules by means of nitrogen introduced by line 33; 14 is a catalyst surge drum; 15 an elutriator; 1 6 a catalyst discard drum; 17 a catalyst make-up drum; 18 a gas lift to be hereinafter described, and 34 a second nitrogen inlet.

Operation is as follows. The hydrocarbon mixture comprising, for example, xylene vapours at a temperature of about 450 C. is introduced through line 19 to the isomerization reactor inwhich it is brought into contact in countercurrent flow with granular isomerization catalyst, e. g.-a'lumina/silica gel, descending under gravity from the catalyst surge'drum 14. The isomerization product is removed through line 20 and is after condensation treated in known manner for extraction of p-xylene, and if desired for removal e.g. by distillation of other components, the residue together with fresh feed being vaporised, preheated and recycled to the reactor through line 19. i

a The catalyst granules move continuously from reactor 11 through the cylindrical chamber 12 in which they are stripped of adhering hydrocarbons and volatile tar by means of inert gas introduced at the base through line 33, and pass to the first section 1 of the regenerating system. The oxidising gas for the regenerative system is fed in two streams, that for the regenerators 1, 2 and 3, being fed through line 21, and that for regenerator 4 through line 22. r The gas stream entering through 21 contains 2.1% of oxygen, is at about 400 C., flows co-currently with the granules, and reduces the carbon content of the granules entering 3 from about 0.2% to about 0.05% by weight. The gas is'disengaged from the granules at the bottom of 3 and passes by line 23 through heat exchanger 9, in which it is cooled to the desired degree indirectly, either by the reaction products or by fresh regenerating gas; while the granules fall by gravity into the fourth vessel 4.

The cooled gas from 9 passes through vessels-2 and 1 in turn also in co-current flow, is heat exchanged in 10 and leaves the system by line 27. The oxygen contentl of the gas entering 2 by line 24 is about 20.3% and its temperature about 350 C: the carbon content of the granules m2 is reduced from about 0.4 to 0.2% by weight. 7 f

The regenerating gas from 10 enters the first regenerator 1 by line 26 with an oxygen content of about 18.3% and at about 350C and the carbon content of the granules are elevated as a suspended stream at, high velocity e.g. about ft./sec. through pipe 30 into the elutriator 15. The granules are passed to surge drum 14 prior to re-use in the reactor 11, or, if a purge of catalyst, on account of reduced activity, is required, to vessel 16 by line.32.. .Material that has become reduced in size by attrition is rejected through line 31. Fresh catalyst granules are in troducedby way of catalyst make-up drum 17.

As a further feature the invention comprises apparatus adapted for catalytic chemical reactions in which is used a granular catalyst moving .countercurrently to the reactants through the reaction zone under the action of gravity which catalyst is continuously regenerated in cocurrent flow with regenerating gas, comprising in vertical descending series a cylindrical'catalyst drum provided with a conical bottom; a cylindrical reactor provided with conical top and bottom portions and provided adjacent to the. top and bottom of the cylindrical portion with gas distributing and gas disengaging devices respectively comprising horizontal plates with pendant downcomers; a tubular stripping zone; at least 3 regenerating units of similar design to the reactor, the gas inlet therefor being in the. distributing zone of the bottom one, and there being pipes in which cooling elements are located connecting the gas disengaging zone of each to the gas distributing zone of that above suchthat in these vessels the same regenerating gas is used serially; a bottom regenerating unit of similar design. to the others provided with a separate gas inlet to its gas distributing zone and a separate gas take offline atits gas disengaging zone; a line feeding from-said bottom regenerating unit to a vertical gas lift pipe for elevating thev catalyst granules to an elutriator situated on a higher levelthan the catalyst reservoir; a pipe for removing reject undersize granules from the elutria tor; and vertical pipes connecting each of the vertical serial units for flow of the granules through each of them in turn. Preferably thereare provided inlet pipes for an inert gas such as nitrogen under a pressure slightly above that in the reactor: the first between the catalyst drum and the, reactor, the second between the reactor and the first regenerator at the bottom of the said stripping zone What is claimed is:

, 1. A process for the continuous regeneration into active condition .of a granular catalyst which has become coated with carbonaceous material, comprising flowing the catalyst under gravity through a first zone wherein it is treated with an inert gas to free it from reactants, thereafter flowing the catalyst sequentially under gravity through at least three separate regeneration zones, and flowing a stream of regenerating oxidizing gas co-currently with said catalyst through each of said regeneration zones, said, gas being cooled intermediate said zones, the sole supply ofregenerating gas being introduced to the bottommost re'generation zone and thetinle t regenerating gas carbonaceous material burnt off in each zone being controlled by the composition, proportion and temperature of said oxidizing gas so that the maximum catalyst temperature is maintained below a temperature which would be injurious to said catalyst.

2. A process as claimed in claim 1 in which the granular catalyst to be regenerated is one which has become coated with carbonaceous material in the isomerization of xylenes, the amount of carbonaceous material is not more than 1% by weight thereof said maximum catalyst temperature being maintained below 550 C.

3. A process for the continuous regeneration into active condition of a granular catalyst which has become coated with carbonaceous material, said catalyst comprising beads of silica and alumina, the carbon content of the catalyst being about 1%, which comprises flowing said catalyst under gravity through a first zone wherein it is treated with an inert gas to free it from reactants, thereafter flowing the catalyst sequentially under gravity through at least three separate regeneration zones, introducing regenerating gas comprising air containing about 21% oxygen and at a temperature of about 400 C. into the bottommost regeneration zone and flowing it therethrough co-currently with said catalyst, whereby .the carbon content of said catalyst is reduced from about 0.2% to about 0.05% and the oxygen content of said regenerating gas is reduced to about 20.3%, said regenerating gas being withdrawn from said Zone and cooled to a temperature of about 350 C., and thereafter introducing said cooled regenerating gas into the next higher zone and flowing it co-currently with the catalyst therethrough, whereby the carbon content of said catalyst is reduced from about 0.4% to about 0.2% and the oxygen content of said gas is reduced to about 18.3%, withdrawing the regenerating gas from said second highest zone and cooling said gas to about 350 C., and thereafter introducing the gas into the uppermost zone and flowing it co-currently with said catalyst therethrough, whereby the carbon content of said catalyst is reduced from about 1% to about 0.4%, the catalyst temperature and amount of carbonaceous material burnt off in each said zone being controlled by the composition, proportion and temperature of said regenerating gas so that the maximum catalyst temperature is maintained below 550 C., the sole supply of said regenerating gas being that introduced to said bottommost regeneration zone.

References Qited in the file of this patent UNITED STATES PATENTS 2,390,708 Hemminger Dec. 1, 1945 2,414,373 Gerhold Jan. 14, 1947 2,457,837 Simpson et a1. Jan. 4, 1949 2,506,545 Crowley May 2, 1950 2,548,295 Fahnestock Apr. 10, 1951 2,550,727 Shimp May 1, 1951 2,592,479 Sinclair Apr. 8, 1952 2,626,857 Crowley Jan. 27, 1953 2,684,930 Berg July 27, 1954 2,701,785 Lechtaler Feb. 8, 1955 

1. A PROCESS FOR THE CONTINUOUS REGENERATION INTO ACTIVE CONDITION OF A GRANULAR CATALYST WHICH HAS BECOME COATED WITH CARNACEOUS MATERIAL, COMPRISING FLOWING THE CATALYST UNDER GRAVITY THROUGH A FIRST ZONE WHEREIN IT IS TREATED WITH AN INERT GAS TO FREE IT FROM REACTANTS, THEREAFTER FLOWING THE CATALYST SEQUENTIALLY UNDER GRAVITY THROUGH AT LEAST THREE SEPARATE REGENERATION ZONES, AND FLOWING A STREAM OF REGENERATION OXIDIZING GAS CO-CURRENTLY WITH SAID CATALYST THROUGH EACH OF SAID REGENERATION ZONES, SAID GAS BEING COOLED INTERMEDIATE SAID ZONES, THE SOLE SUPPLY OF REGENERATION GAS BEING INTRODUCED TO THE BOTTOMMOST REGENERATION ZONE AND THE INLET REGENERATION GAS FOR EACH HIGHER ZONE CONSISTING OF THE OUTLET GAS FROM THE NEXT LOWER ZONE, THE CATALYST TEMPERATURE AND AMOUNT OF CARNONACEOUS MATERIAL BURNT OFF IN EACH ZONE BEING CONTROLLED BY THE COMPOSITION, PROPORTION AND TEMPERATURE OF SAID OXIDIZING GAS SO THAT THE MAXIMUM CATALYST TEM- 